Anthraquinone thiophene and senenophene carboxylic acid compounds



STAT 1 s PATENT FF UNITE ANTHRAQUIN ONE THIOPHEN E AND SENE- V NOPHEN CARBOXYLIC ACID COMPOUNDS Ralph N. Lulek, Waukesha, and Clarence F. Belcher, South Milwaukee, Wis., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del, a corporation of Delaware No Drawing. Application September 30, 1936, Serial No. 103,348

6 Claims. (Cl. 260-53) This invention relates to the preparation of boxylic acid is filtered oiT, washed with 20% salt new anthraquinone thiophene and selenophene solution and purified by redissolving in water and carboxylic acid compounds of the general formula filtering.

Y The acid is precipitated by acidification of the 1' 2' filtrate. It may be further purified by recrystal- 5 M lization from trichlorobenzene. The product has 7 8 9 1 H the following probable formula I 0 SCCOOH II 10 /g /v/ v H 4 V 10 0 wherein Y stands for sulfur or selenium and X stands for OH or a halogen atom. A)

The object of the invention is to provide new acid chlorides of the anthraquinone series which Emample 2 15 are useful as dyestuif intermediates and which, among other uses, may be condensed with amino 10 parts of anthraquinone'zl'thiophene'z" antmaqujnone compounds to produce new at carboxylic acid are Suspended in parts of dye tuffs of good fastne s properties trichlorobenzene and parts of thionyl chloride 20 t is a further bj t of t invention to added. The mixture is heated to YO-80 for one 20 vide a, process for preparing anth a i q hour under agitation and then cooled. The thiophene-(or selenophene)2-carboxy1ic acid nthraquinone-ZJ-thiophene-2'-carboxyl1c acid compounds, thereby making available new acids chloride is filtered ofi, washed with trichlorobenand acid chlorides of the anthraquinone thiophene Zene and alcohol and dried- It is a Y w and selenophene eries for dyestufi manufactur crystalline powder and dissolves in sulfuric acid and for use Wherever sulfur or selenium contain- With a brownish ing anthraquinone compounds of the thiophene Example 3 and selenophene series are desired.

According to our invention anthraquinone-2,1- Q thiophene-(orselenophene) 2-carboxy1icacid may 200 alcohol m a Vessel p q Wlth be prepared by reacting a l-chloroanthraquinoneflux conqenser; Under good agltatlon 16 Parts Z-acrylic acid (obtained by the process described ofometalhc sodium are adde d gradually at 50 to in German Patent 282,265) with an alkali-metal 70 when all sodmm has reacted 18 polysulfide or selenide under atmospheric presmore 58191111191 powder are added to the sure or in an autoclave, to produce the correspond- Sodlum selemde solutlon so folfmed fl fl ing alkali-metal salt of the acid. The alkalifor one'half hour- The selemde Solution 15 metal salt may then be converted to the free acid luted with 100 of Water and parts of or acid halide b the usual methods em lo ed for ch]0m?'anthmquinoneacryfic acid are added preparing free 5: as and their acid g and agitated at the reflux temperature for four 40 hours (microscopic examination shows fine yellow 40 The following examples are given to more fully illustrate the preferred methods for preparing needl es) h mass is cooledfilqered and washed these acids and acid halides. The parts used are alkah'fre? with 10% Salt Solution, The crud? by Weight anthraquinone 2,l selenophene 2 carboxylic Example 1 acid sodium salt 18 dissolved in hot water, the solution filtered hot. (The residue may be ex- 45 10 parts of 1-chloroanthraquinone-2-acry1ic tracted a second time if necessary.) The cooled acid (obtained according to German Patent 282,- filtrate is acidified with dilute hydrochloric acid. 265, by heating 1-chloroanthraquinone-Z-alde- The precipitate is collected, washed and dried. hyde with sodium acetate in acetic anhydride) Example 4 are dissolved in 50 parts of Water with addition of 50 sodium hydroxide. To the clear solution are then 10 parts of anthraquinone-2,1-selenophene-2'- added '70 parts of sodium sulfide solution (18- carboxylic acid are suspended in 100 parts of 20%) and 6 parts of sulfur, and the mass is boiled ortho-dichlorobenzene. 9 parts of phosphorous for several hours. After cooling, the sodium salt pentachloride are added and the whole is stirred of the new anthraquinone-2,1-thiophene-2'-carand warmed at -100 C. for one hour. It is 55.

18 parts of powdered selenium are slurried in then cooled, filtered, and washed with dichlorobenzene, alcohol, and ether, and dried. The anthraquinone-2,1-selenophene-2'-carboxylic acid chloride is a yellow crystalline powder. It dissolves in concentrated sulfuric acid with a yellowish brown color.

The anthraquinone-2,1-thiopheneand selenophene2'-carbo-xylic acids may be converted by any of the usual methods to the acid halides, such as by treatment with phosphorous pentachloride in various organic solvents, or thionyl' bromide, phosphorous pentabromide, etc.

This application is a continuation-in-part of copending application Serial No. 27,814'fi1ed June 21, 1935.

We claim:

1. An anthraquinone carboxylic acid compound of the general formula (W YCCOX 2. Anthraquinone-2,1(S) -thiophene-2'-carboxylic acid chloride.

3. Anthraquinone-2,1 (Se) -selenophene-2-carboxylic acid chloride.

4. In the process for preparing compounds of the class consisting of anthraquinone-2,1(S)- thiophene-2-carboxylic acid and anthraquinone- 2,1(Se)--selenophene-2-carboxylic acid, the step which comprises heating to reaction temperature a 1-ch.loroanthraquinone-2-acrylic acid in alkaline solution with a compound of the class consisting of alkali-metal polysulfides and selenides.

5. The process for the preparation of compounds of the class consisting of anthraquinone- 2,1(S)-thiophene-2'-carboxy1ic acid chloride and anthraquinone-2,1(Se) selenophene -2- carboxylic acid chloride which comprises heating to reaction temperature a l-chloroanthraquinone- Z-acrylic. acid in alkaline solution with a compound of the class consisting of alkali-metal polysulfides and selenides, and reacting the resulting carboxylic acid with an acid chloride forming agent.

6. In the process for preparing anthraqui'none- 2,1(Se) -selenophene-2-carboxylic acid, the step which comprises heating to reaction temperature a l-chloroanthraquinone-Z-acrylic acid in alkaline solution with alkali-metal polyselenide.

RALPH N. LULEK. CLARENCE F. BELCHTER. 

